Reactive anthraquinone colorant compounds and polymeric materials reacted therewith

ABSTRACT

Disclosed are blue, diol anthraquinone blue colorant compounds having excellent thermal stability and which can be reacted into or copolymerized with polyester thus providing a blue-colored polyesters useful for manufacturing a variety of shaped articles such as photographic film base, particularly roentgenographic (X-ray) film. Also disclosed are blue anthraquinone colorant compounds which contain two ethylenically-unsaturated (vinyl), photopolymerizable radicals which may be derived from the aforesaid diol anthraquinone compounds. The anthraquinone colorant compounds containing two ethylenically-unsaturated may be reacted into or copolymerized (or cured) with ethylenically-unsaturated monomers to produce colored vinyl polymers.

FIELD OF THE INVENTION

[0001] The present invention pertains to certain novel blue, diolanthra-quinone blue colorant compounds having excellent thermalstability and which can be reacted into or copolymerized with polyesterthus providing a blue-colored polyesters useful for manufacturing avariety of shaped articles such as photographic film base, particularlyroentgenographic (X-ray) film. This invention also pertains to certainnovel blue anthraquinone colorant compounds which contain twoethylenically-unsaturated (vinyl), photo-polymerizable radicals whichmay be derived from the aforesaid diol anthraquinone compounds. Theanthraquinone colorant compounds containing twoethylenically-unsaturated may be reacted into or copolymerized (orcured) with ethylenically-unsaturated monomers to produce colored vinylpolymers.

BACKGROUND

[0002] X-ray film typically contains a blue colorant to facilitate theperception of the photographic image. The blue-tinted film bases serveto prevent the disadvantages with roentgenographic materials in which aphotographic emulsion is provided on both surfaces of the film supportand wherein a filter desensitization action results in that thephotographic images have a yellow fog or haze, thus interfering with theimage definition. It is desirable that the blue colorant (or toner) hasa minimum light absorbance in the short wavelength region in the visiblelight absorption spectrum, particularly in the 400-450 nm range so thatno additional yellow color be introduced into the film. Blue colorantsfor X-ray film also should be thermally stable, soluble in thepolyester, resistant to sublimation and stable to conditions that may beencountered during storage, such as high humidity. The colorant musthave no adverse effect upon the gelatin-silver halide emulsion coatedonto the blue-colored film base.

[0003] It is known to use various blue anthraquinone colorant compoundsto impart the necessary blue hue to the polyester, e.g., poly(ethyleneterephthalate), particularly 1,4-bis(2′,6′-dialkylanilino)anthraquinonecompounds as well as blue anthraquinone dyes containing hydroxy andarylamino groups. See, for example, the anthraquinone compoundsdisclosed in U.S. Pat. Nos. 3,488,195; 3,849,139; 3,918,976; and3,933,502. In the prior art, the tinted poly(ethylene terephthalate)(PET) is colored by the so-called dope dyeing method which involvesdrying PET pellets, mixing the colorant with the PET, followed byheating the mixture, extruding, stretching and heat-treating the meltand forming it into film. Without the drying step, the startingpolyester will undergo hydrolysis upon heat-melting, which results inpolymer degradation which produces film having inferior and inadequateproperties. The colorant compounds must possess sufficient heatstability to withstand molding or extrusion temperatures as high as 270°C.-300° C. For color control, it also is desirable to prepare amasterbatch by blending PET pellets or chips with the colorant using adry blending method followed by kneading and melt extruding to produce acolored concentrate composition, e.g., a colorant concentration of about1 %. The masterbatch then is mixed with additional uncolored PET pelletsand melt blended and extruded to produce a polyester, typically in theform of pellets, having a total colorant content of about 100-400 partsper million be weight (ppmw).

[0004] In the coloring process described above, it is necessary, ofcourse, to use a colorant that can be readily dispersed and dissolved ina polyester to achieve uniformity during the extrusion process, sincethe film support must have a high degree of transparency and becompletely free of optical imperfections. Problems associated with theabove-described process include sublimation and volatility problemsencountered during the extruding and heat stretching steps, resulting inloss of colorant and contamination of equipment and surrounding areas.Also, when a masterbatch is required to achieve uniformity, the stepadded by formation of the masterbatch increases the costs to the overallcoloration process. In either case, the required handling of dry powdercolorant is hazardous and results in unavoidable contamination problems.Furthermore, uniformity problems are encountered unless melt blendingand extruding times are extended to ensure adequate mixing andsolubilization of the colorant.

[0005] It also is known to color polyesters such as PET by adding thecolorants during the polyester preparation step, e.g., as described inU.S. Pat. No. 3,488,195, column 2, lines 43-45. Such addition of acolorant during polyester synthesis occasions longer periods of time athigh temperature causing more pronounced problems of colorant volatilityresulting in loss of dye by sublimation. Also, colorants having higherthermal stability are needed. Furthermore, the blue anthraquinone dyeshaving aromatic hydroxy groups and arylamino groups change shadesusually toward green under polyester manufacturing conditions,presumably as a result of metalization, rendering the resulting coloredpolyester unsuitable for use in manufacturing X-ray film.

[0006] U.S. Pat. No. 5,372,864 discloses certain1,4-bis(2′,6′-dialkylanilino)-anthraquinone colorant compoundssubstituted with sulfonamide groups which contain polyester-reactivegroups and which have been copolymerized into polyesters at low levels.Efforts to utilize the disclosed reddish-blue colorants of Formula IU.S. Pat. No. 5,372,864 to color polyesters by copolymerization duringpolyester manufacture have provided colored polyesters wherein the bluecolorant is too hypsochromic, i.e., too red, in color to be suitable astoners or colorants for X-ray film and require the addition of secondcolorant compound such as a cyan phthalocyanine, e.g., as described inU.S. Pat. No. 5,744,294. WO 92/13921 discloses various functionalizedchromophores, including anthraquinone colorant compounds and thecopolymerization of the functionalized chromophores into polyesters toprepare color concentrates. The color concentrates are used as colorantsfor a variety of thermoplastic polymeric materials including polyesters.However, WO 92/13921 does not describe any anthraquinone colorantcompound which is suitable for the tinting or coloration of X-ray film.Similarly, Solvent Blue 45 having the formula:

[0007] has been proposed as a colorant for X-ray film. However, SolventBlue 45 also is too red and greener blue dyes are recommended forshading to produce a more neutral blue colorant system. See, forexample, Japanese patent documents JP 55-038825 A2 and JP 62-061065 B4.The addition of a second dye, of course, greatly contributes to thedifficulty of color control.

[0008] As stated above, the present invention also pertains to certainnovel blue anthraquinone colorant compounds which contain at least twoethylenically-unsaturated, photopolymerizable radicals which may bereacted into or copolymerized (or cured) with ethylenically-unsaturatedmonomers to produce colored vinyl polymers. It is known (J.S.D.C., April1977, pp 114-125) to produce colored polymeric materials by combining areactive polymer such as terepolymers having epoxy groups orpolyacryloyl chloride with anthraquinone dyes containing nucleophilicreactive groups such as amino or hydroxy groups; to graftacryloylaminoanthraquinone dyes to the backbone of vinyl or divinylpolymers; and to polymerize anthraquinone dyes containing certainolefinic groups to produce polymeric dyes/pigments. U.S. Pat. No.4,115,056 describes the preparation of blue, substituted1,4-diaminoanthraquinone dyes containing one acryloyloxy group and theuse of the dyes in coloring various fibers, especially polyamide fibers.U.S. Pat. No. 4,943,617 discloses liquid crystalline copolymerscontaining certain blue, substituted1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an olefinic groupcopolymerized therein to provide liquid crystal copolymers having highdichromism. U.S. Pat. No. 5,055,602 describes the preparation of certainsubstituted 1,4-diaminoanthraquinone dyes containing polymerizableacryloyl and methacryloyl groups and their use in coloring polyacrylatecontact lens materials by copolymerizing.

[0009] U.S. Pat. No. 5,362,812 discloses the conversion of a variety ofdye classes, including anthraquinones, into polymeric dyes by (a)polymerizing 2-alkenylazlactones and reacting the polymer with dyescontaining nucleophilic groups and by (b) reacting a nucleophilic dyewith an alkenylazlactones and then polymerizing the freeradically-polymerizable dyes thus produced. The polymeric dyes arereported to be useful for photoresist systems and for colorproofing.U.S. Pat. No. 5,367,039 discloses a process for preparing colored vinylpolymers suitable for inks, paints, toners and the like by emulsionpolymerization of a vinyl monomer with reactive anthraquinone dyesprepared by functionalizing certain anthraquinone dyes with methacryloylgroups.

[0010] U.S. Pat. No. 5,055,602 discloses in Example li, column 7, thevinyl functionalized anthraquinone colorants having the structure:

[0011] This anthraquinone colorant compound exhibits considerable lightabsorption at wavelengths of from 400-450 nm which gives the colorantcompound a green appearance, thus rendering it unsuitable for use as acolorant for typical three component colorant blends useful forproducing the entire range of shades desired. The preparation of avariety of dyes, including some anthraquinones, which containphotopolymerizable groups and their use for color filters suitable foruse in liquid crystal television sets, color copying machines,photosensitive resist resin compositions, and the like are described inU.S. Pat. No. 5,578,419.

SUMMARY OF THE INVENTION

[0012] The present invention is comprised of a plurality of embodimentsthe first of which is a novel class of anthraquinone colorant compoundshaving the formula

[0013] wherein L is a linking group selected from C₂-C₈-alkylene,—(—CH₂CH₂O—)_(n)—CH₂CH₂− and —CH₂-cyclohexylene4—CH₂—, wherein n is 1 or2; and X is hydrogen or the residue of an acylating agent. A secondembodiment of our invention is a molding or extrusion grade polyesterhaving reacted therewith or copolymerized therein at least one of thecompounds of formula (I). The colorant compounds having formula (I) arethermally stable and do not volatilize under polyester manufacturingconditions and do not sublime, exude or migrate from the polyesterduring the film extrusion process or after the film is formed. Thecolorant compounds provide strong absorbance of light at wavelengths offrom about 600 nm to about 650 nm and a minimum of absorbance in the 400nm to about 550 nm range thus providing a pure blue color suitable foruse as an X-ray film toner. A third embodiment of the present inventionpertains to an X-ray film element comprising a film base comprised of apolyester having reacted therewith or copolymerized therein at least oneof the compounds of formula (I).

[0014] A fourth embodiment of the present invention pertains toanthraquinone colorant compounds having the formula:

[0015] wherein L is defined above and Q is a photopolymerizable groupselected from the radicals having the formulae:

[0016] 1 —COC(R₃)═CH—R₄,

[0017] —CONHCOC(R₃)═—CH—R₄,

[0018] —CONH—C₁—C₆-alkylene OCOC(R₃)═CH—R₄,

[0019]  wherein

[0020] R₃ is selected from hydrogen or C₁-C₆-alkyl;

[0021] R₄ is selected from hydrogen; C₁-C₆-alkyl; phenyl; phenylsubstituted with one or more groups selected from C₁-C₆-alkyl,C₁-C₆-alkoxy, —N(C₁-C₆-alkyl)₂, nitro, cyano, C₂-C₆-alkoxycarbonyl,C₂-C₆-alkanoyloxy and halogen; 1- and 2-naphthyl; 1- and 2-naphthylsubstituted with C₁-C₆-alkyl or C₁-C₆-alkoxy; 2- and 3-thienyl; 2- and3-thienyl substituted with C₁-C₆-alkyl or halogen; 2- and 3-furyl; and2- and 3-furyl substituted with C₁-C₆-alkyl;

[0022] R₅ and R₆ are independently selected from hydrogen, C₁-C₆-alkyl,aryl, or R₅ and R₆ may be combined to represent a —(—CH₂—)₃₋₅— radical;

[0023] R₇ is selected from hydrogen or a group selected fromC₁-C₆-alkyl, C₃-C₈-alkenyl, C₃-C₈-cycloalkyl and aryl; and

[0024] R₈ is selected from hydrogen, C₁-C₆ alkyl and aryl.

[0025] The anthraquinone colorant compounds having formula (II) havegood color strength, good solubility in the reactive monomers, goodlight-fastness, and exhibit outstanding thermal stability. They also areneutral blue in color and are very useful in preparing combinationshades with yellow and red colorants compared to known vinylfunctionalized anthraquinone colorants such as those disclosed in U.S.Pat. No. 5,055,602.

[0026] A fifth embodiment of the present invention pertains to a coatingcomposition comprising (i) one or more polymerizable vinyl compounds,(ii) one or more of the colorant compounds of formula (II) describedabove, and (iii) a photoinitiator. A sixth embodiment of the presentinvention pertains to a polymeric composition, typically a coating,comprising a polymer of one or more acrylic acid esters, one or moremethacrylic acid esters and/or other polymerizable vinyl compounds,having copolymerized therein one or more of the colorant compounds offormula (II) described above.

DETAILED DESCRIPTION

[0027] The hydroxy-functionalized, blue, anthraquinone, colorantcompounds of the present have general formula (I):

[0028] wherein L is a linking group selected from C₂-C₈-alkylene,—(—CH₂CH₂O—)_(n)—CH₂CH₂— and —CH₂-cyclohexylene-4-CH₂—, wherein n is 1or 2; and X is hydrogen or the residue of an acylating agent. The term“C₂-C₈-alkylene” is used to denote straight- or branched-chain,divalent, hydrocarbon radicals which contain 2-8 carbon atoms which maybe substituted with at least one group selected from C₁-C₆-alkoxy,halogen, hydroxy, aryl or C₂-C₆-alkanoyloxy. The colorant compounds offormula (I) wherein X is hydrogen may be acylated to produce polyesterreactive groups. Examples of the acylating agent residues which X mayrepresent include —OCOC₁-C₆-alkyl, —OCO₂C₁-C₆-alkyl, —COC₁-C₆-aryl and—CONHC₁-C₆-alkyl and —CONH-aryl, wherein C₁-C₆ alkyl and aryl aredefined below. L preferably is selected from —CH₂CH₂— or —CH₂CH(CH₃)—and X is hydrogen.

[0029] The terms “C₁-C₆-alkoxy” and “C₂-C₆-alkanoyloxy” are used torepresent the groups -O-C₁-C₆-alkyl and —OCOC-C₆-alkyl, respectively,wherein “C₁-C₆-alkyl” denotes a saturated hydrocarbon which contains 1-6carbon atoms, which may be straight- or branch-chained, unsubstituted orsubstituted with one or more groups selected from halogen, C₁-C₆-alkoxysuch as methoxy and ethoxy, phenyl, hydroxy, and C₂-C₆-alkanoyloxy suchas acetyloxy and propionyloxy. The term “halogen” refers to fluorine,chlorine, bromine and iodine with chlorine and bromine being thepreferred halogen atoms. The term “aryl” is used to represent phenyl andphenyl substituted with C₁-C₆-alkyl, C₁-C₆-alkoxy and halogen.

[0030] The colorant compounds of Formula (I) may be prepared accordingto a plurality of procedures generally known to those skilled in theart. For example, 1,4-bis-(2,6-dimethyl4-hydroxyanilino)anthraquinone offormula (III) may be reacted with: (A) an alkanol halide (IV) accordingto Scheme A; (B) an epoxide (V) according to Scheme B; or, preferably,(C) an alkylene carbonate (VI) according to Scheme C.

[0031] In Scheme A, the reactive alkanol halide (IV), i.e., wherein Y ishalogen, preferably is an alkanol chloride, bromide or iodide. TheScheme A reaction typically is carried out in polar aprotic solventssuch as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC),N-methyl-2-pyrrolidinone (NMP), sulfolane, and the like, in the presenceof a base such as alkali metal carbonates, alkali metal bicarbonates,tertiary amines or cyclic nitrogen-containing compounds such as1,5-diazabicyclo[4.3.0]-non-5-ene (DBN),1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and the like. The reaction maysometimes be facilitated by the presence of a catalytic amount of analkali metal bromide, alkali metal iodide and/or conventional phasecatalysts, e.g., tetraalkylammonium halides such as a chloride orbromide. The reactions usually are carried out at temperatures betweenabout 50° C. and about 150° C., preferably about 90° C. to about 125° C.

[0032] In Scheme B, anthraquinone compound (III) is reacted with anepoxide (V), wherein R₁ is H, CH₃, CH₂OH or aryl, using known reactionconditions for reacting aromatic hydroxy groups such as phenolic groupswith epoxides. The reaction normally is carried out in the presence of abase to produce the aromatic phenoxide anion which then is reacted withthe desired epoxide at temperatures of from about 0° C. to 100° C. inthe presence of solvents which do not react with the epoxides underthese reaction conditions. In Scheme C, anthraquinone compound (III) isreacted with an alkylene carbonate (VI), wherein R₂ is H or CH₃ toproduce colorants I. This route is preferable to Schemes A and B becauseit circumvents the handling of haloalkanol and epoxides that are, ingeneral, more toxic than the alkylene carbonates. These reactions arefacilitated by the presence of bases such as those mentioned above forScheme A and/or by the presence of an alkali metal halide,tetraalkylammonium halide or tetraalkylammonium hydroxide. The reactionstypically are carried out by heating intermediate (III) with at leasttwo molecular equivalent amounts of ethylene or propylene carbonate.Excess alkylene carbonate also may be used as the solvent or aco-solvent may be added. In particular, ethylene glycol and propyleneglycol have been found to be effective co-solvents for the preparationof (II). Temperatures of from about 100° C. to about 175° C. normallyare employed, with temperatures of from about 125° C. to about 160° C.being preferable.

[0033] The polyester component of the second embodiment of the presentinvention, i.e., a molding or extrusion grade polyester having reactedtherewith or copolymerized therein at least one of the compounds offormula (I), may be any thermoplastic polyester having an inherentviscosity of at least about 0.4 d/g. Typical molding or extrusion gradepolyester compositions are comprised of:

[0034] (i) diacid residues comprising at least 75 mole percentterephthalic acid residues;

[0035] (ii) diol residues comprising at least 75 mole percent ethyleneglycol residues, wherein the total diacid residues and total diolresidues each equals 100 mole percent; and

[0036] (iii) colorant residues of at least one of the anthraquinonecompounds of formula (I).

[0037] Up to 25 mole percent of the diacid residues and/or diol residuesmay be represented by one or more diacid and/or diol residues other thanterephthalic acid and ethylene glycol residues. Examples of other diacidresidues which may be used include isophthalic acid,1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,succinic acid, glutaric acid, adipic acid, sebacic acid,1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid and otherknown dicarboxylic acids residues. The diacid residues may be derivedfrom the diacid form of the dicarboxylic acid or from functionalderivatives thereof such as the dimethyl, diethyl, bis-(2-hydroxyethyl),or dipropyl ester of the dicarboxylic acid. The anhydrides or acidhalides of these acids also may be employed where practical.

[0038] Examples of alternative diol residues which may be present in thepolyesters include residues derived from 1,4-cyclohexanedimethanol,1,2-propanediol, 1,3-propanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol,Z,8-bis(hydroxymethyl)-tricyclo-[5.2.1.0]decane wherein Z represents 3,4, or 5; and diols containing one or more oxygen atoms in the chain,e.g., diethylene glycol, triethylene glycol, dipropylene glycol,tripropylene glycol and the like. In general, these diols contain 2 to18, preferably 2 to 8 carbon atoms. Cycloaliphatic diols can be employedin their cis or trans configuration or as mixtures of both forms. Thepolyesters are linear, thermoplastic, film grade compositions usuallyhaving an inherent viscosity (I.V.) of about 0.4 to about 1.2 d/gmeasured at 25° C. in a 60/40 ratio by weight ofphenol/tetrachloroethane. The preferred polyester is unmodifiedpoly(ethylene terephthalate) and poly(ethylene terephthalate) modifiedwith up to about 5 mole percent (of a total of 200 mole percent) ofdiacid residues and/or diol residues other than terephthalic acid and/orethylene gylcol residues.

[0039] The linear polyesters may be prepared according topolyester-forming conditions well known in the art. For example, amixture of one or more dicarboxylic acids, preferably aromaticdicarboxylic acids, or ester forming derivatives thereof, and one ormore diols may be heated in the presence of esterification and/orpolyesterification catalysts at temperatures in the range of about 150°C. to about 300° C., and pressures of atmospheric to about 0.2 mm Hg.Normally, the dicarboxylic acid or derivative thereof is esterified ortransesterified with the diol(s) at atmospheric pressure and at atemperature at the lower end of the specified range. Polycondensationthen is effected by increasing the temperature and lowering the pressurewhile excess diol is removed from the mixture.

[0040] Typical catalyst or catalyst systems for polyester condensationare well-known in the art. For example, the catalysts disclosed in U.S.Pat. Nos. 4,025,492; 4,136,089; 4,176,224; 4,238,593; and 4,208,527,incorporated herein by reference, are examples of the catalysts whichmay be used in the preparation of the colored polyester compositions ofthe present invention. Additional polyester condensation catalysts aredescribed by R. E. Wilfong, Journal of Polymer Science, 54(385), 1961. Apreferred temperature range for a polyester condensation is about 260°C. to about 300° C.

[0041] The colored polyester composition constituting the secondembodiment of the present invention colorant residues of at least one ofthe anthraquinone compounds of formula (I). The concentration of thecolorant residues in the colored polyester compositions may varysubstantially, e.g., about 100 ppmw to 5 weight percent, based on thetotal weight of the polyester composition, of the colorant residues. Thepolyester compositions useful for conversion directly into X-ray filmbase, e.g., by conventional extrusion methods, typically contain about100 ppmw to 500 ppmw, preferably about 150 to about 300 ppmw of thecopolymerized blue colorant compound, based on the total weight of thecolored polyester composition. The colored polyester compositionincludes color concentrate compositions wherein the polyester describedabove contains higher levels of the residues of at least one colorantcompound of formula (I), e,g, about 0.05 to 2 weight percent, based onthe total weight of the polyester color concentrate composition. Thiscolor concentrate may be used to color the described polyester by meltblending and extruding to provide a colored X-ray or photographic filmbase preferably containing about 100 to 500 ppmw, most preferably about150 to about 300 ppmw.

[0042] The third embodiment of the present invention concerns a shapedor extruded article prepared from one of the colored polyestercompositions described above. More specifically, the third embodiment isrepresented by an X-ray film element comprising a film base comprised ofa polyester having reacted therewith or copolymerized therein at leastone of the compounds of formula (I), i.e., containing the residue of atleast one of the compounds of formula (I). The preferred film basecontains about 100 to 500 ppmw, most preferably about 150 to about 300ppmw based on the weight of the polyester and colorant residues.

[0043] The fourth embodiment of the present invention concerns novelanthraquinone colorant compounds having the formula:

[0044] in L is a linking group selected from C₂-C₈-alkylene,—(—CH₂CH₂O—)_(n)—CH₂CH₂— and —CH₂-cyclohexylene-4-CH₂—, wherein n is 1or 2; and Q is a photopolymerizable group selected from organic radicalshaving the formulae:

[0045] 1 —COC(R₃)═CH—R₄,

[0046] 2 —CONHCOC(R₃)═CH—R₄,

[0047] 3 —CONH—C₁-C₆-alkylene OCOC(R₃)═CH—R₄,

[0048]  wherein

[0049] R₃ is selected from hydrogen or C₁-C₆-alkyl;

[0050] R₄ is selected from hydrogen; C₁-C₆-alkyl; phenyl; phenylsubstituted with one or more groups selected from C₁-C₆-alkyl,C₁-C₆-alkoxy, —N(C₁-C₆-alkyl)₂, nitro, cyano, C₂-C₆-alkoxycarbonyl,C₂-C₆-alkanoyloxy and halogengen; 1- and 2-naphthyl; 1- and 2-naphthylsubstituted with C₁-C₆-alkyl or C₁-C₆- alkoxy; 2- and 3-thienyl; 2- and3-thienyl substituted with C₁-₆-alkyl or halogen; 2- and 3-furyl; and 2-and 3-furyl substituted with C₁-₆-alkyl;

[0051] R₅ and R₆ are independently selected from hydrogen, C₁-C₆-alkyl,aryl, or R₅ and R₆ may be combined to represent a —(—CH₂—₃₋₅- radical;

[0052] R₇ is selected from hydrogen or a group selected fromC₁-C₆-alkyl, C₁-₈-alkenyl, C₃-C₈-cycloalkyl and aryl; and

[0053] R₈ is selected from hydrogen, C₁-C₆ alkyl and aryl. Q preferablyis a group having the formula —COC(R₃)═CH₂ or

[0054]  wherein R₃ is hydrogen or methyl.

[0055] As used in the above definition of the radicals represented by Q,the terms “C₁-C₆-alkyl”, “C₁-C₆-alkoxy”, “C₂-C₆-alkanoyloxy”, “aryl” and“halogen” have the meaning given above. The term “C₂-C₆-alkoxycarbonyl”refers to the group —CO₂C₁-C₅-alkyl. The term “C₃-C₈-alkenyl” designatesan aliphatic hydrocarbon radical containing at least one double bond andfrom three to eight carbon atoms. The term C₃-C₈-cycloalkyl refers to asaturated cyclic hydrocarbon radical containing three to eight carbonatoms.

[0056] The vinyl-functionalized colorant compounds of formula (II) areprepared by reacting the blue diol compounds of formula (I) with anacylating agents having formulae 1′-9′:

[0057] 140 CICOC(R₃)═CH—R₄ OR O[COC(R₃)═CH—R₄]₂,

[0058] 2′ O═C═N-COC(R₃)═CH—R₄,

[0059] 3′O═C=N-C₁-C₆ alkylene OCOC(R₃)═CH—R₄,

[0060]  wherein R₃, R₄, R₅, R₆, R₈ are defined above.

[0061] The anthraquinone colorant compounds of formula (II) whichcontain vinyl or substituted vinyl groups are polymerizable orcopolymerizable, preferably by free radical mechanisms, said freeradicals being generated by exposure to UV light by methods known in theart of preparing UV-cured resins. Polymerization can be facilitated bythe addition of photoinitiators. The colored polymeric materialsnormally are prepared by dissolving the functionalized colorantscontaining copolymerizable groups in a polymerizable vinyl monomer withor without another solvent and then combining with an oligomeric orpolymeric material which contains one or more vinyl or substituted vinylgroups.

[0062] The fifth embodiment of the present invention is a coatingcomposition comprising (i) one or more polymerizable vinyl compounds,i.e., vinyl compounds which are copolymerizable with the colorantcompounds of formula (II), (ii) one or more of the colorant compounds offormula (II), and (iii) at least one photoinitiator. The polymerizablevinyl compounds useful in the present invention contain at least oneunsaturated group capable of undergoing polymerization upon exposure toUV radiation in the presence of a photoinitiator, i.e., the coatingcompositions are radiation-curable. Examples of such polymerizable vinylcompounds include acrylic acid, methacrylic acid and their anhydrides;crotonic acid; itaconic acid and its anhydride; cyanoacrylic acid andits esters; esters of acrylic and methacrylic acids such as allyl,methyl, ethyl, n-propyl, isopropyl, butyl, tetrahydrofurfuryl,cyclohexyl, isobornyl, n-hexyl, n-octyl, isooctyl, 2-ethylhexyl, lauryl,stearyl, and benzyl acrylate and methacrylate; and diacrylate anddimethacrylate esters of ethylene and propylene glycols, 1,3-butyleneglycol, 1,4-butanediol, diethylene and dipropylene glycols, triethyleneand tripropylene glycols, 1,6-hexanediol, neopentyl glycol, polyethyleneglycol, and polypropylene glycol, ethoxylated bisphenol A, ethoxylatedand propoxylated neopentyl glycol; triacrylate and trimethacrylateesters of tris-(2-hydroxyethyl)isocyanurate, trimethylolpropane,ethoxylated and propoxylated trimethylolpropane, pentaerythritol,glycerol, ethoxylated and propoxylated glycerol; tetraacrylate andtetramethacrylate esters of pentaerythritol and ethoxylated andpropoxylated pentaerythritol; acrylonitrile; vinyl acetate; vinyltoluene; styrene; N-vinyl pyrrolidinone; alpha-methyl-styrene;maleate/fumarate esters; maleic/fumaric acid; crotonate esters, andcrotonic acid.

[0063] The polymerizable vinyl compounds useful in the present inventioninclude polymers which contain unsaturated groups capable of undergoingpolymerization upon exposure to UV radiation in the presence of aphotoinitiator. The preparation and application of these polymerizablevinyl compounds are well known to those skilled in the art as described,for example, in Chemistry and Technology of UV and EB Formulation forCoatings, Inks, and Paints, Volume II: Prepolymers and ReactiveDiluents, G. Webster, editor, John Wiley and Sons, London, 1997.Examples of such polymeric, polymerizable vinyl compounds includeacrylated and methacrylated polyesters, acrylated and methacrylatedpolyethers, acrylated and methacrylated epoxy polymers, acrylated ormethacrylated urethanes, acrylated or methacrylated polyacrylates(polymethacrylates), and unsaturated polyesters. The acrylated ormethacrylated polymers and oligomers typically are combined withmonomers which contain one or more acrylate or methacrylate groups,e.g., monomeric acrylate and methacrylate esters, and serve as reactivediluents. The unsaturated polyesters, which are prepared by standardpolycondensation techniques known in the art, are most often combinedwith either styrene or other monomers, which contain one or moreacrylate or methacrylate groups and serve as reactive diluents. A secondembodiment for the utilization of unsaturated polyesters that is knownto the art involves the combination of the unsaturated polyester withmonomers that contain two or more vinyl ether groups or two or morevinyl ester groups (WO 96/01283, WO 97/48744, and EP 0 322 808).

[0064] The coating compositions of the present invention optionally maycontain one or more added organic solvents if desired to facilitateapplication and coating of the compositions onto the surface ofsubstrates. Typical examples of suitable solvents include, but are notlimited to ketones, alcohols, esters, chlorinated hydrocarbons, glycolethers, glycol esters, and mixtures thereof. Specific examples include,but are not limited to acetone, 2-butanone, 2-pentanone, ethyl acetate,propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate,ethylene glycol diacetate, ethyl 3-ethoxypropionate, methyl alcohol,ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol,ethylene glycol, propylene glycol, ethylene glycol monomethyl ether,ethylene glycol monoethyl ether, ethylene glycol monopropyl ether,ethylene glycol monobutyl glycol, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,propylene glycol monomethyl ether, diethylene glycol monobutyl etheracetate, diethylene glycol monoethyl ether acetate, ethylene glycolmonobutyl ether acetate, propylene glycol monomethyl ether acetate,methylene chloride, chloroform, and mixtures thereof. The amount ofadded or extraneous solvent which may be present in our novel coatingcompositions may be in the range of about 1 to 70 weight percent, moretypically about 1 to 25 weight percent, based on the total weight of thecoating composition.

[0065] Certain polymerizable vinyl monomers may serve as both reactantand solvent. These contain at least one unsaturated group capable ofundergoing polymerization upon exposure to UV radiation in the presenceof a photoinitiator. Specific examples include, but are not limited to:methacrylic acid, acrylic acid, ethyl acrylate and methacrylate, methylacrylate and methacrylate, hydroxyethyl acrylate and methacrylate,diethylene glycol diacrylate, trimethylolpropane triacrylate, 1,6hexanediol di(meth)acrylate, neopentyl glycol diacrylate andmethacrylate, vinyl ethers, divinyl ethers such as diethyleneglycoldivinyl ether, 1,6-hexanediol divinyl ether, cyclohexanedimethanoldivinyl ether, 1,4-butanediol divinyl ether, triethyleneglycol divinylether, trimethylolpropane divinyl ether, and neopentyl glycol divinylether, vinyl esters, divinyl esters such as divinyl adipate, divinylsuccinate, divinyl glutarate, divinyl 1,4-cyclohexanedicarboxylate,divinyl 1,3-cyclohexanedicarboxylate, divinyl isophthalate, and divinylterephthalate, N-vinyl pyrrolidone, and mixtures thereof.

[0066] In addition, the compositions of the present invention may bedispersed in water rather than dissolved in a solvent to facilitateapplication and coating of the substrate surface. In the water-dispersedcompositions of the present invention a co-solvent is optionally used.Typical examples of suitable cosolvents include but are not limited toacetone, 2-butanone, methanol, ethanol, isopropyl alcohol, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, ethyleneglycol monopropyl ether, and ethylene glycol monobutyl ether, ethyleneglycol, and propylene glycol. Typical examples of water-solubleethylenically unsaturated solvents include but are not limited to:methacrylic acid, acrylic acid, N-vinyl-pyrrolidone, 2-ethoxyethylacrylate and methacrylate, polyethylene glycol dimethacrylate,polypropylene glycol monoacrylate and monomethacrylate, and mixturesthereof. The amount of suitable aqueous organic solvent (i.e., organicsolvent and water) in the dispersed coating compositions of the presentinvention is about 10 to about 90 weight percent, preferably about 75 toabout 90 weight percent of the total coating composition.

[0067] The coating compositions of the present invention contain one ormore of the reactive anthraquinone colorant compounds of formula (II).The concentration of the colorant compound or compounds may be fromabout 0.005 to 30.0, preferably from about 0.05 to 15.0, weight percentbased on the weight of the polymerizable vinyl compound(s) present inthe coating composition, i.e., component (i) of the coatingcompositions. The coating compositions of the present invention normallycontain a photoinitiator. The amount of photoinitiator typically isabout 1 to 15 weight percent, preferably about 3 to about 5 weightpercent, based on the weight of the polymerizable vinyl compound(s)present in the coating composition. Typical photoinitiators includebenzoin and benzoin ethers such as marketed under the tradenames ESACUREBO, EB1, EB3, and EB4 from Fratelli Lamberti; VICURE 10 and 30 fromStauffer; benzil ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one(IRGACURE 651), 2-hydroxy-2-methyl-1-phenylpropan-1′-one (IRGACURE1173), 2-methyl-2-morpholino-1-(p-methylthiophenyl)propan-1-one(IRGACURE 907), alpha-hydroxyalkylphenones such as(1-hydroxycyclohexyl)(phenyl)methanone (IRGACURE 184),2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (IRGACURE369), 2-hydroxy-2-methyl-1′-phenylpropan-1-one IRGACURE 1173) from CibaGeigy, Uvatone 8302 by Upjohn; alpha, alpha-dialkoxyacetophenonederivatives such as DEAP and UVATONE 8301 from Upjohn; DAROCUR 116,1173, and 2959 by Merck; and mixtures of benzophenone and tertiaryamines In pigmented coating compositions, the rate of cure can beimproved by the addition of a variety of phosphine oxide photoinitiaterssuch as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irganox 819),Irgacure 819, 1700, and 1700 and phosphine oxide mixtures such as a50/50 by weight mixtures of IRGACURE 1173 and2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR 4265) from Ciba.Further details regarding such photoinitiators and curing procedures maybe found in the published literature such as U.S. Pat. No. 5,109,097,incorporated herein by reference. Depending upon the thickness of thecoating (film), product formulation, photoinitiator type, radiationflux, and source of radiation, exposure times to ultraviolet radiationof about 0.5 second to about 30 minutes (50-5000 mJ/square cm) typicallyare required for curing. Curing also can occur from solar radiation,i.e., sunshine.

[0068] The coating compositions of the present invention may contain oneor more additional components typically present in coating compositions.Examples of such additional components include leveling, rheology, andflow control agents such as silicones, fluorocarbons or cellulosics;flatting agents; pigment wetting and dispersing agents; surfactants;ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments;defoaming and antifoaming agents; anti-settling, anti-sag and bodyingagents; anti-skinning agents; anti-flooding and anti-floating agents;fungicides and mildewcides; corrosion inhibitors; thickening agents;and/or coalescing agents. The coating compositions of the presentinvention also may contain non-reactive modifying resins. Typicalnon-reactive modifying resins include homopolymers and copolymers ofacrylic and methacrylic acid; homopolymers and copolymers of alkylesters of acrylic and methacrylic acid such as methyl, ethyl, n-propyl,isopropyl, butyl, tetrahydrofurfuryl, cyclohexyl, isobornyl, n-hexyl,n-octyl, isooctyl, 2-ethylhexyl, lauryl, stearyl, and benzyl acrylateand methacrylate; acrylated and methacrylated urethane, epoxy, andpolyester resins, silicone acrylates, cellulose esters such as celluloseacetate butyrates, cellulose acetate, propionates, nitrocellulose,cellulose ethers such as methyl cellulose, ethyl cellulose,hydroxypropyl cellulose, and hydroxypropyl methyl cellulose.

[0069] Typical plasticizers include alkyl esters of phthalic acid suchas dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutylphthalate, and dioctyl phthalate; citrate esters such as triethylcitrate and tributyl citrate; triacetin and tripropionin; and glycerolmonoesters such as Eastman 18-04, 18-07, 18-92 and 18-99 from EastmanChemical Company. Specific examples of additional additives can be foundin Raw Materials Index, published by the National Paint & CoatingsAssociation, 1500 Rhode Island Avenue, N.W., Washington, D.C. 20005.

[0070] The sixth embodiment of the present invention pertains to apolymeric composition, typically a polymeric coating, comprising apolymer of one or more acrylic acid esters, one or more methacrylic acidesters and/or other polymerizable vinyl compounds, having copolymerizedtherein one or more of the anthraquinone colorant compounds of formula(II). The colored polymeric compositions provided by our invention maybe prepared from the coating compositions described above and typicallycontain from about 0.005 to 30.0 weight percent, preferably from about05 to 15.0 weight percent, of the reactive or polymerized residue of oneor more of the colorant compounds of formula (II) based on the weight ofthe composition or coating. The novel polymeric coatings may have athickness of about 2.5 to 150 microns, more typically about 15 to 65microns.

[0071] The polymeric coatings of the present invention typically have asolvent resistance of at least 100 MEK double rubs using ASTM ProcedureD-3732; preferably a solvent resistance of at least about 200 doublerubs. Such coatings also typically have a pencil hardness of greaterthan or equal to F using ASTM Procedure D-3363; preferably a pencilhardness of greater than or equal to H. The coating compositions can beapplied to substrates with conventional coating equipment. The coatedsubstrates are then exposed to radiation such as ultraviolet light inair or in nitrogen which gives a cured finish. Mercury vapor or Xenonlamps are applicable for the curing process. The coatings of the presentinvention can also be cured by electron beam.

[0072] The radiation-curable coating compositions of this invention aresuitable as adhesives and coatings for such substrates as metals such asaluminum and steel, plastics, glass, wood, paper, and leather. On woodsubstrates the coating compositions may provide both overall transparentcolor and grain definition. Various aesthetically-appealing effects canbe achieved thereby. Due to reduced grain raising and higher filmthicknesses, the number of necessary sanding steps in producing afinished wood coating may be reduced when using the colored coatingcompositions of the invention rather than conventional stains. Coatingcompositions within the scope of our invention may be applied toautomotive base coats where they can provide variousaesthetically-appealing effects in combination with the base coats andcolor differences dependent on viewing angle (lower angles create longerpath lengths and thus higher observed color intensities). This mayprovide similar styling effects as currently are achieved with metalflake orientation in base coats.

[0073] Various additional pigments, plasticizers, and stabilizers may beincorporated to obtain certain desired characteristics in the finishedproducts. These are included in the scope of the invention.

Example

[0074] The anthraquinone colorant compounds, polyester compositions andcoating compositions provided by the present invention are furtherillustrated by the following examples.

EXAMPLE 1

[0075] A mixture of1,4-bis(2′,6′-dimethyl-4′-hydroxyanilino)anthraquinone (4.78 g, 0.01mol) (U.S. Pat. No. 3,918,976), potassium iodide (3.0 g), potassiumcarbonate (1.38 g), ethylene carbonate (10.6 g, 0.12 m) and ethyleneglycol (35 mL) was heated and stirred at about 150° C. for about onehour in an oil bath. Thin-layer chromatography (50/50tetrahydrofuran/cyclohexane) showed one blue spot that had a lower Rfvalue and no spot for starting material. After being cooled, thereaction mixture was treated with methanol and stirred to precipitatethe blue product, which was collected by filtration, washed withmethanol, washed with hot water and then washed again with methanol tofacilitate drying. The blue colorant weighed 3.49 g (62% of thetheoretical yield) and field desorption mass spectral analysis confirmedthe structure:

[0076] Additional examples (Examples 2-10) of the anthraquinone colorantcompounds of formula (I) are presented in Table I. TABLE I Example No.—L— 2 —CH₂CH(OH)— 3 —CH₂C(CH₃)₂CH₂— 4 —CH₂CH(C₆H₅)— 5 —CH₂CH₂CH₂— 6CH₂₄ 7 —CH₂CH₂OCH₂CH₂— 8 CH₂CH₂O)₂CH₂CH₂— 9 —CH₂CH(OH)CH₂— 10—CH₂C₆H₁₀-4-CH₂—

Example 11

[0077] The following materials were placed in a 500 mL, three-necked,round-bottom flask:

[0078] 97.0 g (0.50 mol) dimethyl terephthalate

[0079] 62.0 g (1.0 mol) ethylene glycol

[0080] 2.0 mL of an n-butanol solution containing 0.3 g of titaniumtetraisopropoxide per 100 mL of solution;

[0081] 3.1 mL of an ethylene glycol solution containing 0.79 g ofantimony triacetate per 100 mL of solution; and

[0082] 0.0288 g of blue colorant of Example 1 (300 ppm).

[0083] The flask was equipped with a nitrogen inlet, stirrer, vacuumoutlet and condensing flask and contents were stirred and heated in aBelmont metal bath for about 45 minutes at 200° C. The temperature wasincreased to about 210° C. for 65 minutes with a nitrogen sweep over thereaction mixture. The temperature was increased to about 268° C. overabout 30 minutes and then 0.40 mL of an ethylene glycol solution of amixed phosphorous ester composition (Merpol A) (0.0914 g Merpol A/mL ofsolution) was added. The pressure was reduced from atmospheric to about120 torr over 5 minutes and held at about 268° C. for 50 minutes.Polycondensation was completed by increasing the temperature to about285° C., reducing the pressure to about 8 torr over 5 minutes, holdingthis temperature and pressure for about 25 minutes, reducing thepressure to about 0.5 torr over about 1 minute and holding for 20minutes. The resulting blue polyester had an inherent viscosity of 0.596as measured in a 60/40 ratio by weight of phenol/tetrachloroethane at aconcentration of 0.5 g per 100 mL. After grinding the polymer in a Wileymill and passing the solid through a 3 mm screen, a blue tinted filmhaving a thickness of 381 micron (15 mil) was prepared by compressionmolding a portion of the polyester composition. No evidence of colorvolitalization or sublimation was noted during the entire polymerizationreaction in the collected distillates comprising methanol and ethyleneglycol. The film has desirable light transmission properties for use asa blue tinted X-ray film base.

Comparative Example 1

[0084] The procedure of Example I was repeated exactly except that theprior art dye 1,4-bis-2′,6′-diethylanilino)anthraquinone (U.S. Pat. No.3,488,195) was used. In contrast to the colorant of Example I, thiscolorant volatilized and colored the collected distillates blue showingthat this type colorant is unsuitable for addition during polyestermanufacture.

Example 12

[0085] A mixture of1,4-bis(2′,6′-dimethyl-4′-hydroxyanilino)anthraquinone (1.50 g, 3.13mmol) (U.S. Pat. No. 3,918,976), potassium iodide (1.0 g), potassiumcarbonate (0.45 g), propylene carbonate (3.84 g, 37.6 mmol) andpropylene glycol (15 ml) was stirred and heated at 150° C. for about 2.5hours. The mixture was allowed to cool to room temperature and methanol(50 ml) was added followed by 50 ml of water. The product was collectedby filtration, washed with water and dried in air (yield 1.6, 95% oftheory). FDMS supported the following expected structure:

Example 13

[0086] A portion (0.6 g, 1 mmol) of the diol colorant from Example 12,3-isopropenyl-α,α-dimethylbenzyl isocyanate (0.5 g), toluene (15 ml) anddibutyltin laurate (2 drops) were mixed and heated together withstirring to about 90° C. and held at 90° C. for about 2.0 hours. Whilestill hot, heptane (30 ml) was added and the mixture was allowed tocool. No solid precipitated so the mixture was poured into anevaporating dish and solvent was allowed to evaporate leaving asemi-solid, dark blue product which solidified upon treatment with someheptane. The solid product was separated from the heptane by filtration,washed with heptane, and dried in air (yield=0.75 g, 75.3% of theory).FDMS supported the structure:

Example 14-31

[0087] Additional examples of the vinyl functionalized anthraquinonecolorant compounds of formula (II) are presented in Table II. TABLE IIExample No. L Q 14 —CH₂CH₂— —COC(CH₃)═CH₂ 15 —CH₂CH₂——CONHC(CH₃)₂-1,3-C₆H₄— C(CH₃)═CH₂ 16 —CH₂CH(CH₃)— —COC(CH₃)═CH₂ 17—CH₂CH(CH₃)— —COCH═CH₂ 18 —CH₂CH₂— —COCH═CH₂ 19 —CH₂CH₂CH₂— —COCH═CH—CH₃20 —CH₂CH(OH)CH₂— —COCH═CH—C₆H₅ 21 —CH₂CH(C₆H₅)—

22

23 —CH₂CH₂OCH₂CH₂— —COC(CH₃)═CH₂ 24

—CONHC(CH₃)₂-1,3-C₆H₄—C(CH₃)═CH₂ 25

—COCH═CH—CO₂H 26 —CH₂CH_(2—) —CO-1,4-C₆H₄—CH═CH₂ 27 —CH₂CH₂——COC(CH₃)₂NHCOC(CH₃)═CH₂ 28 —CH₂CH₂— —CONHCOC(CH₃)═CH₂ 29 —CH₂CH₂—

30 —CH₂CH₂— —COCH₂C═(CH₂)CO₂CH₃ 31 —CH₂CH₂— —COCH═CH—CO₂C₂H₅

[0088] Samples of the coating compositions may be used to coat glassplates using a knife blade. The wet film thickness typically is about 15to 75 microns (0.6 to 3.0 mils). Any solvent present is evaporated togive a clear, somewhat tacky film. Prior to exposure to UV radiation,each film is readily soluble in organic solvents. The dried film on theglass plate is exposed to UV radiation from a 200 waft per inch mediumpressure mercury vapor lamp housed in an American Ultraviolet Companyinstrument using a belt speed of 25 ft. per minute. One to five passesunder the lamp normally provides a crosslinked coating with maximumhardness and solvent resistance.

[0089] Each cured coating (film) may be evaluated for Konig PendulumHardness (ASTM D4366 DIN 1522), solvent resistance by the methyl ethylketone double-rub test, and solubility in acetone before and afterexposure to UV radiation. The damping time for Konig Pendulum Hardnesson uncoated glass is 250 seconds; coatings with hardness above 100seconds are generally considered hard coatings. The methyl ethyl ketone(MEK) double rub test is carried out in accordance with ASTM ProcedureD-3732 by saturating a piece of cheese cloth with methyl ethyl ketone,and with moderate pressure, rubbing the coating back and forth. Thenumber of double rubs is counted until the coating is removed. Theacetone solubility test is carried out by immersing a dry, pre-weighedsample of the cured film in acetone for 48 hours at 25° C. The film isremoved, dried for 16 hours at 60° C. in a forced-air oven, andreweighed. The weight percent of the insoluble film remaining iscalculated from the data.

[0090] The coatings and coating compositions provided by the presentinvention and the preparation thereof are further illustrated by thefollowing example. A colored, photopolymerizable composition wasprepared by thoroughly mixing 0.5 g the blue dye of Example 13 with acoating composition consisting of 20 g Jägalux UV1500 polyesteracrylate, 10 g of bisphenol A epoxy acrylate, 9 g dipropyleneglycoldiacrylate (DPGDA), 7 g trimethylolpropane triacrylate (TMPTA), and 4 gof Darocure 1173 photoinitiator using a small Cowles mixer until thecomponents were completely dispersed. The resulting coating compositioncontaining 1% of the blue colorant compound is drawn down with a wirewound rod to provide a 25.4 micron (1 mil) thick coating on an oak woodpanel. This panel is passed through a UV cure machine at a speed of 6.1meters per minute (20 feet/minute) using a lamp with an intensity of118.1 wafts per cm (300 wafts per inch). Konig Pendulum Hardnessmeasurements (ASTM D4366 DIN 1522) conducted on the coated paneltypically show no significant loss of hardness due to incorporation ofthe dye.

[0091] The invention has been described in detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be effected within the spirit andscope of the invention.

We claim:
 1. A copolymerizable, thermally stable, blue anthraquinonecolorant compound having the formula:

wherein L is a linking group selected from C₂-C₈-alkylene,—(—CH₂CH₂O—)_(n)—CH₂CH₂— and —CH₂-cyclohexylene-4-CH₂—, wherein n is 1or 2; and X is hydrogen or the residue of an acylating agent.
 2. Ananthraquinone colorant compound according to claim 1 wherein X ishydrogen or the residue of an acylating agent having the formula—OCOC₁-C₆-alkyl, —OCO₂C₁-C₆-alkyl, —COC₁-C₆-aryl and —CONHC₁-C₆-alkyland —CONH-aryl.
 3. An anthraquinone colorant compound according to claim1 wherein X is hydrogen.
 4. An anthraquinone colorant compound accordingto claim 1 wherein L is —CH₂CH₂— or —CH₂CH(CH₃)— and X is hydrogen.
 5. Amolding or extrusion grade polyester composition comprising a polyesterhaving an inherent viscosity of at least 0.4 having reacted therewith orcopolymerized therein at least one of the anthraquinone colorantcompounds defined in claim
 1. 6. A molding or extrusion grade polyestercomposition according to claim 5 having an inherent viscosity of about0.4 to 1.2 comprising: (i) diacid residues comprising at least 75 molepercent terephthalic acid residues; (ii) diol residues comprising atleast 75 mole percent ethylene glycol residues, wherein the total diacidresidues and total diol residues each equals 100 mole percent; and (iii)colorant residues of at least one of the anthraquinone compounds havingthe formula:

 wherein L is a linking group selected from C₂-C₈-alkylene,—(—CH₂CH₂O—)_(n)—CH₂CH₂— and —CH₂-cyclohexylene-4-CH₂—, wherein n is 1or 2; and X is hydrogen or the residue of an acylating agent.
 7. Amolding or extrusion grade polyester composition according to claim 6wherein L is —CH₂CH₂— or —CH₂CH(CH₃)—, X is hydrogen, the concentrationof the colorant residues is about 100 to 500 ppmw, and the polyester isselected from unmodified poly(ethylene terephthalate) and poly(ethyleneterephthalate) modified with up to about 5 mole percent of diacidresidues and/or diol residues other than terephthalic acid and/orethylene gylcol residues.
 8. A molding or extrusion grade polyestercomposition according to claim 6 wherein L is —CH₂CH₂— or —CH₂CH(CH₃)—,X is hydrogen, the concentration of the colorant residues is about 0.05to 2 weight percent, and the polyester is selected from unmodifiedpoly(ethylene terephthalate) and poly(ethylene terephthalate) modifiedwith up to about 5 mole percent of diacid residues and/or diol residuesother than terephthalic acid and/or ethylene gylcol residues.
 9. AnX-ray film element comprising a film base comprised of a polyesterhaving reacted therewith or copolymerized therein at least one of thecompounds of formula (I).
 10. The X-ray film element of claim 9 whereinthe polyester has an inherent viscosity of about 0.4 to 1.2 andcomprises: (i) diacid residues comprising at least 75 mole percentterephthalic acid residues; (ii) diol residues comprising at least 75mole percent ethylene glycol residues, wherein the total diacid residuesand total diol residues each equals 100 mole percent; and (iii) 100 to500 ppmw colorant residues of at least one of the anthraquinonecompounds having the formula:

 wherein L is a linking group selected from C₂-C₈-alkylene,—(—CH₂CH₂O—)_(n)—CH₂CH₂— and —CH₂-cyclohexylene-4-CH₂—, wherein n is 1or 2; and X is hydrogen or the residue of an acylating agent.
 11. TheX-ray film element of claim 10 wherein wherein L is —CH₂CH₂— or—CH₂CH(CH₃)—, X is hydrogen, the concentration of the colorant residuesis about 150 to 300 ppmw, and the polyester is selected from unmodifiedpoly(ethylene terephthalate) and poly(ethylene terephthalate) modifiedwith up to about 5 mole percent of diacid residues and/or diol residuesother than terephthalic acid and/or ethylene gylcol residues.
 12. Ananthraquinone colorant compound having the formula:

wherein L is a linking group selected from C₂-C₈-alkylene,—(—CH₂CH₂O—)_(n)—CH₂CH₂— and —CH₂-Cyclohexylene-4-CH₂—, wherein n is 1or 2; and Q is a photopolymerizable group selected from the radicalshaving the formulae 1 —COC(R₃)═CH—R₄, 2 —CONHCOC(R₃)═CH—R₄, 3—CONH—C₁-C₆-alkylene OCOC(R₃)═CH—R₄,

 wherein R₃ is selected from hydrogen or C₁-C₆-alkyl; R₄ is selectedfrom hydrogen; C₁-C₆-alkyl; phenyl; phenyl substituted with one or moregroups selected from C₁-C₆-alkyl, C₁-C₆-alkoxy, —N(C₁-C₆-alkyl)₂, nitro,cyano, C₂-C₆-alkoxycarbonyl, C₂-C₆-alkanoyloxy and halogen; 1- and2-naphthyl; 1- and 2-naphthyl substituted with C₁-C₆-alkyl orC₁-C₆-alkoxy; 2- and 3-thienyl; 2- and 3-thienyl substituted withC₁-C₆-alkyl or halogen; 2- and 3-furyl; and 2- and 3-furyl substitutedwith C₁-C₆-alkyl; R₅ and R₆ are independently selected from hydrogen,C₁-C₆-alkyl, aryl, or R₅ and R₆ may be combined to represent a—(—CH₂—)₃₋₅— radical; R₇ is selected from hydrogen or a group selectedfrom C₁-C₆-alkyl, C₃-C₈-alkenyl, C₃-C₈-cycloalkyl and aryl; and R₈ isselected from hydrogen, C₁-C₆ alkyl and aryl.
 13. An anthraquinonecolorant compound according to claim 12 wherein Q is a group having theformula —COC(R₃)═CH₂ or

wherein R₃ is hydrogen or methyl.
 14. An anthraquinone colorant compoundaccording to claim 12 wherein L is —CH₂CH₂— or —CH₂CH(CH₃)— and Q is agroup having the formula —COC(R₃)═CH₂ or

wherein R₃ is hydrogen or methyl.
 15. A coating composition comprising(i) one or more polymerizable vinyl compounds, (ii) one or more of thecolorant compounds according to claim 12, and (iii) at least onephotoinitiator.
 16. A coating composition according to claim 15comprising (i) one or more polymerizable vinyl compounds, (ii) one ormore of the colorant compounds of claim 12 present in a concentration ofabout 0.05 to 15 weight percent based on the weight of component (i),and (iii) a photoinitiator present in a concentration of about 1 to 15weight percent based on the weight of the polymerizable vinylcompound(s) present in the coating composition.
 17. A coatingcomposition according to claim 16 wherein the polymerizable vinylcompounds comprise a solution of a polymeric, polymerizable vinylcompound selected from acrylated and methacrylated polyesters, acrylatedand methacrylated polyethers, acrylated and methacrylated epoxypolymers, acrylated or methacrylated urethanes, and mixtures thereof, ina diluent selected from monomeric acrylate and methacrylate esters. 18.A polymeric coating composition according to claim 15 comprising apolymer of one or more acrylic acid esters, one or more methacrylic acidesters and/or other copolymerizable vinyl compounds, havingcopolymerized therein one or more of the colorant compounds having theformula:

wherein L is —CH₂CH₂— or —CH₂CH(CH₃)—; and Q is a photopolymerizablegroup selected from the radicals having the formulae 1 —COC(R₃)═CH—R₄, 2—CONHCOC(R₃)═CH—R₄, 3 —CONH—C₁-C₆-alkylene OCOC(R₃)═CH—R₄,

 wherein R₃ is selected from hydrogen or C₁-C₆-alkyl; R₄ is selectedfrom hydrogen; C₁-C₆-alkyl; phenyl; phenyl substituted with one or moregroups selected from C₁-C₆-alkyl, C₁-C₆-alkoxy, —N(C₁-C₆-alkyl)₂, nitro,cyano, C₂-C₆-alkoxycarbonyl, C₂-C₆-alkanoyloxy and halogen; 1- and2-naphthyl; 1- and 2-naphthyl substituted with C₁-C₆-alkyl orC₁-C₆-alkoxy; 2- and 3-thienyl; 2- and 3-thienyl substituted withC₁-₆-alkyl or halogen; 2- and 3-furyl; and 2- and 3-furyl substitutedwith C₁-₆-alkyl; R₅ and R₆ are independently selected from hydrogen,C₁-C₆-alkyl, aryl, or R₅ and R₆ may be combined to represent a—(—CH₂—)₃₋₅— radical; R₇ is selected from hydrogen or a group selectedfrom C₁-C₆-alkyl, C₃-₈-alkenyl, C₃-C₈-cycloalkyl and aryl; and R₈ isselected from hydrogen, C₁-C₆ alkyl and aryl.
 19. A polymericcomposition according to claim 18 comprising a coating of an acrylicpolymer of one or more acrylic acid esters, one or more methacrylic acidesters or a mixture thereof having copolymerized therein one or more ofthe colorant compounds defined in claim
 18. 20. A polymeric compositionaccording to claim 18 comprising a coating of an unsaturated polyestercontaining one or more maleate/fumarate residues; one or more monomerswhich contain one or more vinyl ether groups, one or more vinyl estergroups, or a combination thereof, and, optionally, one or more acrylicor methacrylic acid esters; or a mixture thereof having copolymerizedtherein one or more of the colorant compounds defined in claim
 18. 21. Apolymeric coating according to claim 19 containing from about 0.05 to15.0 weight percent of the residue of one or more of the colorantcompounds of claim 18 based on the weight of the coating.